EP0665214B1 - Monocarboxylic acid amides of polyamines - Google Patents

Monocarboxylic acid amides of polyamines Download PDF

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Publication number
EP0665214B1
EP0665214B1 EP95810037A EP95810037A EP0665214B1 EP 0665214 B1 EP0665214 B1 EP 0665214B1 EP 95810037 A EP95810037 A EP 95810037A EP 95810037 A EP95810037 A EP 95810037A EP 0665214 B1 EP0665214 B1 EP 0665214B1
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Prior art keywords
formula
mixture
bis
acid
radical
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EP95810037A
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German (de)
French (fr)
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EP0665214A1 (en
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Dr. Walter Fischer
Christine Helbling
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Huntsman Advanced Materials Switzerland GmbH
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/36—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/38—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a carbon atom of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/41—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/50—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/54—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/54—Amino amides>

Definitions

  • the present invention relates to new monocarboxamides of certain di- and Triamines, curable epoxy resin mixtures containing the new monocarboxamides, and the molding materials obtained from the curable epoxy resin mixtures by curing, especially coatings.
  • liquid polyamines are used as curing agents, such as formulated mixtures based on 4,4'-diaminodiphenylmethane.
  • this hardener applies suspected of being mutagenic and carcinogenic and has been used in the USA, for example, since December 1992 with exceptional application requirements by the state authorities OSHA (Occupational Safety and Health Administration), Final Rule in the Federal Register on the Use of Methylene Dianiline.
  • OSHA Occupational Safety and Health Administration
  • Methylene Dianiline Similarly, it has Swiss Federal Office of Public Health this hardener according to the poison list 1 (1991 edition) classified as toxic * 1 (carcinogenic).
  • Ancamine X2280 Available liquid polyamine based on polycyclic polyamines is suitable for Production of epoxy resin coatings with good chemical resistance, with Exception to carboxylic acids such as acetic acid.
  • the present invention thus relates to monocarboxamides of the formula I containing hydroxyl groups
  • R represents a residue of the formulas is a C 9 -C 19 alkyl, C 9 -C 19 alkenyl or a C 9 -C 19 alkdienyl
  • each R 2 independently of one another represents a hydrogen atom or a C 1 -C 4 alkyl
  • each R 3 each independently represents a hydrogen atom or a hydroxyl group and at least one R 3 represents a hydroxyl group
  • R 1 represents a radical of the formulas stands.
  • R is a radical of the formulas is a C 15 -C 17 alkyl or C 15 -C 17 alkenyl, each R 2 being a tert-butyl, and each R 3 being a hydrogen atom or a hydroxyl group.
  • R in formula I represents the rest of the formula
  • R 1 preferably denotes a radical of the formulas
  • the compounds according to the invention are advantageous amine curing agents for epoxy resins.
  • the present invention thus also relates to a curing agent for epoxy resins, which is characterized in that it contains at least one compound of the formula I.
  • the curing agent according to the invention can be prepared, for example, by using a monocarboxylic acid or its ester of the formula II R ⁇ COOR 4 wherein R has the same meaning as in formula I and R 4 represents a hydrogen atom, C 1 -C 6 alkyl or phenyl, with a di- or triamine of the formula III H 2 N ⁇ R 1 wherein R 1 has the same meaning as in formula I, reacted at elevated temperature, 2 to 10 moles of a compound of formula III being used per mole of a compound of formula II.
  • this reaction is carried out in the temperature range from 80 ° to 200 ° C.
  • the diamine or triamine of the formula III is preferably in one equivalent excess, so that in the implementation essentially the corresponding diaminomonocarboxamides and triaminomonocarboxamides in addition to an excess of di- and triamine.
  • this Reaction products as curing agents it is possible, but not necessary, that To rid the reaction products of the excess diamine or triamine.
  • the implementation of the monocarboxylic acids or their esters with the di- or triamines can also in the presence of additives such as solvents, such as butanol or Xylene, accelerators, for example salicylic acid, nonylphenol, or alkali Alkaline earth perchlorates or nitrates, flexibilizers, for example polyethylene glycols, Flow agents, for example benzyl alcohol, pigments, fillers or antioxidants, be performed.
  • solvents such as butanol or Xylene
  • accelerators for example salicylic acid, nonylphenol, or alkali Alkaline earth perchlorates or nitrates
  • flexibilizers for example polyethylene glycols
  • Flow agents for example benzyl alcohol, pigments, fillers or antioxidants, be performed.
  • the implementation can also be carried out simultaneously or in succession using different di and / or Triamines and various monocarboxylic acids or their esters are carried out, the corresponding product mixtures are obtained.
  • the monocarboxamides according to the invention can be used Hardening of conventional epoxy resins can be used.
  • epoxy resins can also be used in which the 1,2-epoxy groups on different heteroatoms or functional groups are bound; to these connections include, for example, the N, N, O-triglycidyl derivative of 4-aminophenol, the Glycidyl ether-glycidyl ester of salicylic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin or 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane.
  • Epoxy resin (a) a liquid or viscous polyglycidyl ether or ester, in particular a liquid or viscous bisphenol diglycidyl ether.
  • epoxy compounds mentioned above are known and some of them are commercially available. Mixtures of epoxy resins can also be used.
  • the amount of curing agent used depends on the chemical nature of the Hardening agent and according to the desired properties of the curable mixture and of the hardened product. The maximum amount can be easily determined. Usually 0.75 to 1.25 equivalents of hydrogen amine per 1 Epoxy equivalent used.
  • the mixtures according to the invention can be prepared in the customary manner Mix the components by hand or with the help of known ones Mixing units, for example by means of stirrers, kneaders or rollers.
  • the mixtures according to the invention can be the customary ones Additives are added, such as fillers, pigments, dyes, Leveling agents or plasticizers.
  • the mixtures according to the invention are advantageously distinguished by a comparatively lower tendency towards carbonation, that is to say that in the cold and at high atmospheric humidity, the mixtures do not become cloudy due to the absorption of CO 2 from the air and crystal formation after the CO 2 has reacted with the polyamines.
  • the mixtures according to the invention can be hardened in a manner known per se be made in several stages. Hardening generally takes place at Room temperature or below room temperature or by heating the mixtures to temperatures up to 120 ° C, especially at temperatures between 5 and 50 ° C. To ensure good curing of the mixtures according to the invention at low temperatures, to achieve for example between 5 and 50 ° C, the mixtures with Curing accelerators based on tertiary amines and / or phenols and / or Alkali or alkaline earth salts are used, such as 2,4,6-tris (dimethylaminomethyl) phenol, nonylphenol, calcium or magnesium nitrate.
  • Curing accelerators based on tertiary amines and / or phenols and / or Alkali or alkaline earth salts are used, such as 2,4,6-tris (dimethylaminomethyl) phenol, nonylphenol, calcium or magnesium nitrate.
  • Another object of the invention are those by hardening the ones according to the invention Mixtures obtained molding materials or coatings.
  • those produced from the mixtures according to the invention are distinguished Molded materials and coatings due to their high chemical resistance, especially against carboxylic acids, such as aqueous acetic acid with a Acetic acid content up to 30% by weight.
  • This product can be cleaned and isolated as follows: 2.2 g of the green-yellow oil obtained above are boiled out twice with 40 ml of dioxane, the dioxane phases being decanted off hot. By cooling the dioxane phases, decanting and drying under high vacuum, residues are obtained (total 840 mg) which, according to 1 H-NMR and mass spectra, consist of the compound of the above formula (about 67 mol%) and MXDA (about 33 mol -%) exist (2: 1 molecular complex).
  • a mixture of 20.0 g (58.7 mmol) of stearic acid butyl ester, 40.0 g (293.6 mmol) of MXDA and 25.7 g of benzyl alcohol is stirred at 200 ° C. for 15 h, during which part of the butanol formed is distilled off .
  • 83.1 g (> 100% of theory) of a semi-solid product mixture are obtained, which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MXDA, mainly the monoamide of the formula contains.
  • a mixture of 15.0 g (44.0 mmol) of stearic acid butyl ester, 37.5 g (220.2 mmol) of IPD and 22.5 g of benzyl alcohol is stirred at 200 ° C. for 20 hours, part of the butanol formed being distilled off .
  • 71.4 g (> 100% of theory) of a product mixture is obtained which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess IPD, mainly contains the products of the formulas contains.
  • the Persoz hardness rose to 326 s.
  • the layer on the steel plate then resists exposure to 10% aqueous acetic acid for at least three months without pitting or peeling off.
  • the curable mixture described above also cures satisfactorily at 20 ° C./100% relative atmospheric humidity and at 5 ° C./45% relative atmospheric humidity, with no or very little surface haze occurring.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Paints Or Removers (AREA)

Description

Die vorliegende Erfindung betrifft neue Monocarbonsäureamide von bestimmten Di-und Triaminen, härtbare Epoxidharzgemische, enthaltend die neuen Monocarbonsäureamide, und die aus den härtbaren Epoxidharzgemischen durch Härtung erhaltenen Formstoffe, insbesondere Beschichtungen.The present invention relates to new monocarboxamides of certain di- and Triamines, curable epoxy resin mixtures containing the new monocarboxamides, and the molding materials obtained from the curable epoxy resin mixtures by curing, especially coatings.

Zur Herstellung von chemikalienresistenten Beschichtungen auf Basis von Epoxidharzen werden als Härtungsmittel vor allem flüssige Polyamine eingesetzt, wie beispielsweise formulierte Gemische auf Basis von 4,4'-Diaminodiphenylmethan. Dieser Härter gilt aber als mutagen- und kanzerogenverdächtig und wird beispielsweise in USA seit Dezember 1992 mit aussergewöhnlichen Anwendungsauflagen seitens der staatlichen Behörden OSHA (Occupational Safety and Health Administration), Final Rule in the Federal Register on the Use of Methylene Dianiline, belegt. In ähnlicher Weise hat das schweizerische Bundesamt für Gesundheitswesen diesen Härter gemäss Giftliste 1 (Ausgabe 1991) in die Giftklasse 1* (kanzerogen) eingestuft. Es besteht somit ein Bedarf nach anderen aminischen Härtungsmitteln für Epoxidharzbeschichtungen.For the production of chemical-resistant coatings based on epoxy resins liquid polyamines are used as curing agents, such as formulated mixtures based on 4,4'-diaminodiphenylmethane. But this hardener applies suspected of being mutagenic and carcinogenic and has been used in the USA, for example, since December 1992 with exceptional application requirements by the state authorities OSHA (Occupational Safety and Health Administration), Final Rule in the Federal Register on the Use of Methylene Dianiline. Similarly, it has Swiss Federal Office of Public Health this hardener according to the poison list 1 (1991 edition) classified as toxic * 1 (carcinogenic). There is therefore a need for other amine curing agents for epoxy resin coatings.

Ein von der Firma Anchor Chemical unter der Bezeichnung Ancamine X2280 im Handel erhältliches flüssiges Polyamin auf Basis von polycyclischen Polyaminen eignet sich zur Herstellung von Epoxidharzbeschichtungen mit einer guten Chemikalienresistenz, mit Ausnahme gegenüber von Carbonsäuren, wie beispielsweise Essigsäure.One commercially available from Anchor Chemical under the name Ancamine X2280 Available liquid polyamine based on polycyclic polyamines is suitable for Production of epoxy resin coatings with good chemical resistance, with Exception to carboxylic acids such as acetic acid.

Es wurde nun gefunden, dass bestimmte neue Monocarbonsäureamide, die durch Umsetzung von bestimmten Hydroxymonocarbonsäuren oder deren Ester mit bestimmten Di- oder Triaminen erhalten werden, den Epoxidharzbeschichtungen eine bessere Chemikalienresistenz, inbesondere gegenüber Carbonsäuren, verleihen.It has now been found that certain new monocarboxamides by Reaction of certain hydroxymonocarboxylic acids or their esters with certain Di- or triamines are obtained, the epoxy resin coatings a better one Resist chemicals, especially carboxylic acids.

Gegenstand vorliegender Erfindung sind somit hydroxylgruppenhaltige Monocarbonsäureamide der Formel I

Figure 00010001
worin R für einen Rest der Formeln
Figure 00020001
ein C9-C19-Alkyl, C9-C19-Alkenyl oder ein C9-C19-Alkdienyl steht, wobei jedes R2 unabhängig voneinander je ein Wasserstoffatom oder ein C1-C4-Alkyl bedeutet, jedes R3 unabhängig voneinander je ein Wasserstoffatom oder eine Hydroxylgruppe bedeutet und mindestens ein R3 für eine Hydroxylgruppe steht, und R1 für einen Rest der Formeln
Figure 00020002
steht.The present invention thus relates to monocarboxamides of the formula I containing hydroxyl groups
Figure 00010001
where R represents a residue of the formulas
Figure 00020001
is a C 9 -C 19 alkyl, C 9 -C 19 alkenyl or a C 9 -C 19 alkdienyl, where each R 2 independently of one another represents a hydrogen atom or a C 1 -C 4 alkyl, each R 3 each independently represents a hydrogen atom or a hydroxyl group and at least one R 3 represents a hydroxyl group, and R 1 represents a radical of the formulas
Figure 00020002
stands.

Von den erfindungsgemässen hydroxylgruppenhaltigen Monocarbonsäureamiden der Formel I sind solche bevorzugt, worin R für einen Rest der Formeln

Figure 00030001
ein C15-C17-Alkyl oder C15-C17-Alkenyl steht, wobei jedes R2 ein tert.-Butyl bedeutet, und jedes R3 je ein Wasserstoffatom oder je eine Hydroxylgruppe bedeutet.Of the hydroxyl-containing monocarboxamides of the formula I according to the invention, preference is given to those in which R is a radical of the formulas
Figure 00030001
is a C 15 -C 17 alkyl or C 15 -C 17 alkenyl, each R 2 being a tert-butyl, and each R 3 being a hydrogen atom or a hydroxyl group.

Insbesondere bedeutet R in der Formel I den Rest der Formel

Figure 00030002
In particular, R in formula I represents the rest of the formula
Figure 00030002

In den erfindungsgemässen Monocarbonsäureamiden bedeutet R1 vorzugsweise einen Rest der Formeln

Figure 00030003
In the monocarboxamides according to the invention, R 1 preferably denotes a radical of the formulas
Figure 00030003

Wie eingangs erwähnt, stellen die erfindungsgemässen Verbindungen vorteilhafte aminische Härtungsmittel für Epoxidharze dar.As mentioned at the beginning, the compounds according to the invention are advantageous amine curing agents for epoxy resins.

Gegenstand vorliegender Erfindung ist somit auch ein Härtungsmittel für Epoxidharze, das dadurch gekennzeichnet ist, dass es mindestens eine Verbindung der Formel I enthält.The present invention thus also relates to a curing agent for epoxy resins, which is characterized in that it contains at least one compound of the formula I.

Das erfindungsgemässe Härtungsmittel kann beispielsweise hergestellt werden, indem man eine Monocarbonsäure oder deren Ester der Formel II R―COOR4 worin R die gleiche Bedeutung wie in Formel I hat und R4 ein Wasserstoffatom, C1-C6-Alkyl oder Phenyl bedeutet, mit einem Di- oder Triamin der Formel III H2N―R1 worin R1 die gleiche Bedeutung wie in Formel I hat, bei erhöhter Temperatur umsetzt, wobei man auf 1 Mol einer Verbindung der Formel II 2 bis 10 Mole einer Verbindung der Formel III einsetzt.The curing agent according to the invention can be prepared, for example, by using a monocarboxylic acid or its ester of the formula II R ― COOR 4 wherein R has the same meaning as in formula I and R 4 represents a hydrogen atom, C 1 -C 6 alkyl or phenyl, with a di- or triamine of the formula III H 2 N ― R 1 wherein R 1 has the same meaning as in formula I, reacted at elevated temperature, 2 to 10 moles of a compound of formula III being used per mole of a compound of formula II.

Im allgemeinen wird diese Umsetzung im Temperaturbereich von 80° bis 200°C vorgenommen. Vorzugsweise wendet man bei der Umsetzung der Monocarbonsäuren mit den Di- oder Triaminen Temperaturen von 160 bis 200°C und bei der Umsetzung der Monocarbonsäureester mit den Di- oder Triaminen Temperaturen von 100 bis 180°C an.In general, this reaction is carried out in the temperature range from 80 ° to 200 ° C. Preferably used in the reaction of the monocarboxylic acids with the Di- or triamines temperatures of 160 to 200 ° C and in the implementation of the Monocarboxylic acid esters with the di- or triamines at temperatures from 100 to 180 ° C.

Vorzugsweise liegen bei der Umsetzung das Di- oder Triamin der Formel III in einem äquivalenten Überschuss vor, so dass bei der Umsetzung im wesentlichen die entsprechenden Diaminomonocarbonsäureamide und Triaminomonocarbonsäureamide neben einem Überschuss an Di- und Triamin entstehen. Für den Einsatz dieser Umsetzungsprodukte als Härtungsmittel ist es möglich, aber nicht erforderlich, die Umsetzungsprodukte von dem überschüssigen Di- oder Triamin zu befreien.During the reaction, the diamine or triamine of the formula III is preferably in one equivalent excess, so that in the implementation essentially the corresponding diaminomonocarboxamides and triaminomonocarboxamides in addition to an excess of di- and triamine. For using this Reaction products as curing agents it is possible, but not necessary, that To rid the reaction products of the excess diamine or triamine.

Die Umsetzung der Monocarbonsäuren bzw. deren Estern mit den Di- oder Triaminen kann auch in Gegenwart von Zusätzen, wie Lösungsmitteln, beispielsweise Butanol oder Xylol, Beschleunigern, beispielsweise Salicylsäure, Nonylphenol, Alkali-oder Erdalkaliperchlorate oder -nitrate, Flexibilisatoren, beispielsweise Polyethylenglykole, Fliessmittel, beispielsweise Benzylalkohol, Pigmenten, Füllstoffen oder Antioxidatien, durchgeführt werden.The implementation of the monocarboxylic acids or their esters with the di- or triamines can also in the presence of additives such as solvents, such as butanol or Xylene, accelerators, for example salicylic acid, nonylphenol, or alkali Alkaline earth perchlorates or nitrates, flexibilizers, for example polyethylene glycols, Flow agents, for example benzyl alcohol, pigments, fillers or antioxidants, be performed.

Die Umsetzung kann auch gleichzeitig oder nacheinander mit verschiedenen Di-und/oder Triaminen und verschiedenen Monocarbonsäuren oder deren Estern durchgeführt werden, wobei die entsprechenden Produktegemische erhalten werden.The implementation can also be carried out simultaneously or in succession using different di and / or Triamines and various monocarboxylic acids or their esters are carried out, the corresponding product mixtures are obtained.

Die Monocarbonsäuren der Formel II und die Di- und Triamine der Formel III stellen bekannte Verbindungen dar und sind zum Teil im Handel erhältlich.The monocarboxylic acids of formula II and the di- and triamines of formula III known compounds and some are commercially available.

Wie eingangs erwähnt, können die erfindungsgemässen Monocarbonsäureamide zum Härten von üblichen Epoxidharzen eingesetzt werden.As mentioned at the beginning, the monocarboxamides according to the invention can be used Hardening of conventional epoxy resins can be used.

Ein weiterer Gegenstand vorliegender Erfindung sind somit auch härtbare Gemische, enthaltend

  • (a) ein Epoxidharz mit mehr als einer 1,2-Epoxidgruppe im Molekül und
  • (b) mindestens eine erfindungsgemässe Verbindung der Formel I.
    • Another object of the present invention are therefore also curable mixtures containing
  • (a) an epoxy resin with more than one 1,2-epoxy group in the molecule and
  • (b) at least one compound of the formula I according to the invention

    • Als Epoxidharze (a), die in den erfindungsgemässen härtbaren Gemischen eingesetzt werden können, eignen sich die in der Epoxidharztechnik üblichen Epoxidharze. Beispiele für Epoxidharze sind:

  • I) Polyglycidyl- und Poly-(β-methylglycidyl)-ester, erhältlich durch Umsetzung einer Verbindung mit mindestens zwei Carboxylgruppen im Molekül und Epichlorhydrin bzw. β-Methylepichlorhydrin. Die Umsetzung erfolgt zweckmässig in der Gegenwart von Basen.
    Als Verbindung mit mindestens zwei Carboxylgruppen im Molekül können aliphatische Polycarbonsäuren verwendet werden. Beispiele für solche Polycarbonsäuren sind Oxalsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Sebacinsäure, Korksäure, Azelainsäure oder dimerisierte bzw. trimerisierte Linolsäure.
    Es können aber auch cycloaliphatische Polycarbonsäuren eingesetzt werden, wie beispielsweise Tetrahydrophthalsäure, 4-Methyltetrahydrophthalsäure, Hexahydrophthalsäure oder 4-Methylhexahydrophthalsäure.
    Weiterhin können aromatische Polycarbonsäuren Verwendung finden, wie beispielsweise Phthalsäure, Isophthalsäure oder Terephthalsäure.
  • II) Polyglycidyl-oder Poly-(β-methylglycidyl)-ether, erhältlich durch Umsetzung einer Verbindung mit mindestens zwei freien alkoholischen Hydroxygruppen und/oder phenolischen Hydroxygruppen und Epichlorhydrin oder β-Methylepichlorhydrin unter alkalischen Bedingungen, oder in Anwesenheit eines sauren Katalysators und anschliessende Alkalibehandlung.
    Die Glycidylether dieses Typs leiten sich beispielsweise von acyclischen Alkoholen ab, wie von Ethylenglykol, Diethylenglykol und höheren Poly-(oxyethylen)-glykolen, Propan-1,2-diol oder Poly-(oxypropylen)-glykolen, Propan-1,3-diol, Butan-1,4-diol, Poly-(oxytetramethylen)-glykolen, Pentan-1,5-diol, Hexan-1,6-diol, Hexan-2,4,6-triol, Glycerin, 1,1,1-Trimethylolpropan, Pentaerythrit, Sorbit, sowie von Polyepichlorhydrinen. Sie leiten sich aber auch beispielsweise von cycloaliphatischen Alkoholen, wie 1,4-Cyclohexandimethanol, Bis-(4-hydroxycyclohexyl)-methan oder 2,2-Bis-(4-hydroxycyclohexyl)-propan, ab oder sie besitzen aromatische Kerne, wie N,N-Bis-(2-hydroxyethyl)-anilin oder p,p'-Bis-(2-hydroxyethylamino)-diphenylmethan.
    Die Glycidylether können sich auch von einkerningen Phenolen ableiten, wie beispielsweise von Resorcin oder Hydrochinon, oder sie basieren auf mehrkernigen Phenolen, wie beispielsweise Bis-(4-hydroxyphenyl)-methan, 4,4'-Dihydroxybiphenyl, Bis-(4-hydroxyphenyl)-sulfon, 1,1,2,2-Tetrakis-(4-hydroxyphenyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan sowie von Novolaken, erhältlich durch Kondensation von Aldehyden, wie Formaldehyd, Acetaldehyd, Chloral oder Furfuraldehyd, mit Phenolen, wie Phenol, oder mit Phenolen, die im Kern mit Chloratomen oder C1-C9-Alkylgruppen substituiert sind, wie beispielsweise 4-Chlorphenol, 2-Methylphenol, oder 4-tert.-Butylphenol oder durch Kondensation mit Bisphenolen, wie solche der oben genannten Art.
  • III) Poly-(N-glycidyl)-verbindungen, erhältlich durch Dehydrochlorierung der Reaktionsprodukte von Epichlorhydrin mit Aminen, die mindestens zwei Aminwasserstoffatome enthalten. Bei diesen Aminen handelt es sich zum Beispiel um Anilin, n-Butylamin, Bis-(4-aminophenyl)-methan, m-Xylylendiamin oder Bis-(4-methylaminophenyl)-methan. Zu den Poly-(N-glycidyl)-verbindungen zählen aber auch Triglycidylisocyanurat, N,N'-Diglycidylderivate von Cycloalkylenharnstoffen, wie Ethylenharnstoff oder 1,3-Propylenharnstoff, und Diglycidylderivate von Hydantoinen, wie von 5,5-Dimethylhydantoin.
  • IV) Poly-(S-glycidyl)-verbindungen, beispielsweise Di-S-glycidylderivate, die sich von Dithiolen, wie beispielsweise Ethan-1,2-dithiol oder Bis-(4-mercaptomethylphenyl)-ether ableiten.
  • V) Cycloaliphatische Epoxidharze, beispielsweise Bis-(2,3-epoxycyclopentyl)-ether, 2,3-Epoxycyclopentylglycidylether, 1,2-Bis-(2,3-epoxycyclopentyloxy)-ethan oder 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexancarboxylat.
    • The epoxy resins (a) which can be used in the curable mixtures according to the invention are the epoxy resins customary in epoxy resin technology. Examples of epoxy resins are:
  • I) Polyglycidyl and poly (β-methylglycidyl) esters, obtainable by reacting a compound with at least two carboxyl groups in the molecule and epichlorohydrin or β-methylepichlorohydrin. The reaction is conveniently carried out in the presence of bases.
    Aliphatic polycarboxylic acids can be used as a compound having at least two carboxyl groups in the molecule. Examples of such polycarboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, suberic acid, azelaic acid or dimerized or trimerized linoleic acid.
    However, cycloaliphatic polycarboxylic acids can also be used, such as, for example, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
    Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid can also be used.
  • II) Polyglycidyl or poly (β-methylglycidyl) ether, obtainable by reacting a compound with at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and epichlorohydrin or β-methylepichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment .
    The glycidyl ethers of this type are derived, for example, from acyclic alcohols, such as from ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol or poly- (oxypropylene) glycols, propane-1,3-diol , Butane-1,4-diol, poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerin, 1,1,1 -Trimethylolpropane, pentaerythritol, sorbitol and polyepichlorohydrins. However, they are also derived, for example, from cycloaliphatic alcohols, such as 1,4-cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane, or they have aromatic nuclei, such as N. , N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.
    The glycidyl ethers can also be derived from mononuclear phenols, such as, for example, from resorcinol or hydroquinone, or they are based on multinuclear phenols, such as, for example, bis- (4-hydroxyphenyl) methane, 4,4'-dihydroxybiphenyl, bis- (4-hydroxyphenyl) -sulfone, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-) hydroxyphenyl) propane and novolaks, obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols, such as phenol, or with phenols which are substituted in the core with chlorine atoms or C 1 -C 9 -alkyl groups, such as for example 4-chlorophenol, 2-methylphenol, or 4-tert-butylphenol or by condensation with bisphenols, such as those of the type mentioned above.
  • III) Poly (N-glycidyl) compounds, obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines which contain at least two amine hydrogen atoms. These amines are, for example, aniline, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-methylaminophenyl) methane. However, the poly (N-glycidyl) compounds also include triglycidyl isocyanurate, N, N'-diglycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1,3-propylene urea, and diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.
  • IV) Poly (S-glycidyl) compounds, for example di-S-glycidyl derivatives, which are derived from dithiols, such as, for example, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.
  • V) Cycloaliphatic epoxy resins, for example bis (2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether, 1,2-bis (2,3-epoxycyclopentyloxy) ethane or 3,4-epoxycyclohexylmethyl-3 ', 4 'epoxycyclohexane carboxylate.

    • Es lassen sich aber auch Epoxidharze verwenden, bei denen die 1,2-Epoxidgruppen an unterschiedliche Heteroatome bzw. funktionelle Gruppen gebunden sind; zu diesen Verbindungen zählen beispielsweise das N,N,O-Triglycidylderivat des 4-Aminophenols, der Glycidylether-glycidylester der Salicylsäure, N-Glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin oder 2-Glycidyloxy-1,3-bis-(5,5-dimethyl-1-glycidylhydantoin-3-yl)-propan. However, epoxy resins can also be used in which the 1,2-epoxy groups on different heteroatoms or functional groups are bound; to these connections include, for example, the N, N, O-triglycidyl derivative of 4-aminophenol, the Glycidyl ether-glycidyl ester of salicylic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin or 2-glycidyloxy-1,3-bis (5,5-dimethyl-1-glycidylhydantoin-3-yl) propane.

    Bevorzugt verwendet man in den erfindungsgemässen härtbaren Gemischen als Epoxidharz (a) einen flüssigen oder viskosen Polyglycidylether oder -ester, insbesondere einen flüssigen oder viskosen Bisphenoldiglycidylether.Preferably used in the curable mixtures according to the invention as Epoxy resin (a) a liquid or viscous polyglycidyl ether or ester, in particular a liquid or viscous bisphenol diglycidyl ether.

    Die oben genannten Epoxidverbindungen sind bekannt und zum Teil im Handel erhältlich. Es können auch Gemische von Epoxidharzen verwendet werden.The epoxy compounds mentioned above are known and some of them are commercially available. Mixtures of epoxy resins can also be used.

    Die Menge des eingesetzten Härtungsmittels richtet sich nach der chemischen Natur des Härtungsmittels und nach den gewünschten Eigenschaften der härtbaren Mischung und des gehärteten Produktes. Die maximale Menge kann leicht ermittelt werden. Normalerweise werden 0,75 bis 1,25 Äquivalente Aminwasserstoff pro 1 Epoxidäquivalent eingesetzt.The amount of curing agent used depends on the chemical nature of the Hardening agent and according to the desired properties of the curable mixture and of the hardened product. The maximum amount can be easily determined. Usually 0.75 to 1.25 equivalents of hydrogen amine per 1 Epoxy equivalent used.

    Die Herstellung der erfindungsgemässen Gemische kann in üblicher Weise durch Vermischen der Komponenten durch Handrührung oder mit Hilfe bekannter Mischaggregate, beispielsweise mittels Rührer, Kneter oder Walzen, erfolgen.The mixtures according to the invention can be prepared in the customary manner Mix the components by hand or with the help of known ones Mixing units, for example by means of stirrers, kneaders or rollers.

    Je nach Anwendung können den erfindungsgemässen Gemischen die gebräuchlichen Zusätze beigegeben werden, wie beispielsweise Füllstoffe, Pigmente, Farbstoffe, Verlaufmittel oder Plastifizierungsmittel.Depending on the application, the mixtures according to the invention can be the customary ones Additives are added, such as fillers, pigments, dyes, Leveling agents or plasticizers.

    Die erfindungsgemässen Gemische zeichnen sich vorteilhaft durch eine vergleichsweise geringere Carbonatisierungstendenz auf, dass heisst, in der Kälte und bei hoher Luftfeuchtigkeit tritt in den Gemischen keine Trübung durch Aufnahme von CO2 aus der Luft und Kristallbildung nach Umsetzung des CO2 mit den Polyaminen auf.The mixtures according to the invention are advantageously distinguished by a comparatively lower tendency towards carbonation, that is to say that in the cold and at high atmospheric humidity, the mixtures do not become cloudy due to the absorption of CO 2 from the air and crystal formation after the CO 2 has reacted with the polyamines.

    Die Härtung der erfindungsgemässen Gemische kann in an sich bekannter Weise ein-oder mehrstufig vorgenommen werden. Die Härtung erfolgt im allgemeinen bei Raumtemperatur oder unterhalb der Raumtemperatur oder durch Erhitzen der Gemische auf Temperaturen bis zu 120°C, insbesondere bei Temperaturen zwischen 5 und 50°C. Um eine gute Aushärtung der erfindungsgemässen Gemische bei niedrigen Temperaturen, beispielsweise zwischen 5 und 50°C zu erzielen, können die Gemische mit Härtungsbeschleunigern auf Basis von tertiären Aminen und/oder Phenolen und/oder Alkali- oder Erdalkalisalzen eingesetzt werden, wie beispielsweise 2,4,6-Tris-(dimethylaminomethyl)-phenol, Nonylphenol, Calcium- oder Magnesiumnitrat. The mixtures according to the invention can be hardened in a manner known per se be made in several stages. Hardening generally takes place at Room temperature or below room temperature or by heating the mixtures to temperatures up to 120 ° C, especially at temperatures between 5 and 50 ° C. To ensure good curing of the mixtures according to the invention at low temperatures, to achieve for example between 5 and 50 ° C, the mixtures with Curing accelerators based on tertiary amines and / or phenols and / or Alkali or alkaline earth salts are used, such as 2,4,6-tris (dimethylaminomethyl) phenol, nonylphenol, calcium or magnesium nitrate.

    Ein weiterer Gegenstand der Erfindung sind auch die durch Härten der erfindungsgemässen Gemische erhaltenen Formstoffe oder Beschichtungen.Another object of the invention are those by hardening the ones according to the invention Mixtures obtained molding materials or coatings.

    Wie eingangs erwähnt, zeichnen sich die aus den erfindungsgemässen Gemischen hergestellten Formstoffe und Beschichtungen durch eine hohe Chemikalienresistenz, insbesondere gegenüber Carbonsäuren, wie beispielsweise wässriger Essigsäure mit einem Gehalt an Essigsäure bis zu 30 Gew-%, aus.As mentioned at the beginning, those produced from the mixtures according to the invention are distinguished Molded materials and coatings due to their high chemical resistance, especially against carboxylic acids, such as aqueous acetic acid with a Acetic acid content up to 30% by weight.

    Herstellung der Polyaminoamide: Production of the polyaminoamides : Beispiel 1example 1

    97,8 g (304,1 mMol) Ancamine® X2168 (MPCA) und 47,9 g Benzylalkohol werden auf 120°C erwärmt und mit 14,0 g (76 mMol) Gallussäuremethylester versetzt. Das Gemisch wird während 2,5 Stunden (h) bei 160°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 155,0 g (99% der Theorie) eines Produktegemisches erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen MPCA hauptsächlich aus den Monoamiden der Formeln

    Figure 00080001
    und deren Struktur- und Stereoisomeren besteht. 97.8 g (304.1 mmol) of Ancamine® X2168 (MPCA) and 47.9 g of benzyl alcohol are heated to 120 ° C. and 14.0 g (76 mmol) of methyl gallic acid are added. The mixture is stirred at 160 ° C. for 2.5 hours (h), methanol being distilled off. After cooling, 155.0 g (99% of theory) of a product mixture are obtained which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MPCA, mainly consists of the monoamides of the formulas
    Figure 00080001
    and their structural and stereoisomers exist.

    Beispiel 2Example 2

    34,9 g (108,6 mMol) Ancamine® X2168 (MPCA) und 20,6 g Benzylalkohol werden auf 160°C erwärmt. Nach Zugabe von 5,0 g (27,2 mMol) Gallussäuremethylester und 8,05 g (27,2 mMol) Oelsäuremethylester wird das Gemisch während 5 h bei 180°C gerührt. Nach dem Abkühlen werden 62,1 g (93% d. Th.) eines Produktegemisches erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen MPCA hauptsächlich die Monoamide der Formeln

    Figure 00090001
    sowie deren Struktur- und Stereoisomere enthält.34.9 g (108.6 mmol) of Ancamine® X2168 (MPCA) and 20.6 g of benzyl alcohol are heated to 160 ° C. After adding 5.0 g (27.2 mmol) of methyl gallic acid and 8.05 g (27.2 mmol) of methyl oleic acid, the mixture was stirred at 180 ° C. for 5 h. After cooling, 62.1 g (93% of theory) of a product mixture are obtained which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MPCA, mainly contains the monoamides of the formulas
    Figure 00090001
    as well as their structural and stereoisomers.

    Beispiel 3Example 3

    42,3 g (131,4 mMol) Ancamine® X2168 (MPCA) und 24,5 g Benzylalkohol werden auf 160°C erwärmt. Nach Zugabe von 5,0 g (32,9 mMol) 4-Hydroxybenzoesäuremethylester und 9,74 g (32,9 mMol) Oelsäuremethylester wird das Gemisch während 7,5 h bei 180°C gerührt. Nach dem Abkühlen werden 77,1 g (97% d. Th.) eines Produktegemisches erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen MPCA hauptsächlich die Monoamide der Formeln

    Figure 00100001
    sowie deren Struktur- und Stereoisomere enthält.42.3 g (131.4 mmol) of Ancamine® X2168 (MPCA) and 24.5 g of benzyl alcohol are heated to 160 ° C. After adding 5.0 g (32.9 mmol) of methyl 4-hydroxybenzoate and 9.74 g (32.9 mmol) of methyl oleic acid, the mixture was stirred at 180 ° C. for 7.5 h. After cooling, 77.1 g (97% of theory) of a product mixture are obtained which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MPCA, mainly contains the monoamides of the formulas
    Figure 00100001
    as well as their structural and stereoisomers.

    Beispiel 4Example 4

    57,4 g (421,6 mMol) m-Xylylendiamin (MXDA) und 25 g (84,3 mMol) Oelsäuremethylester werden vermischt und während 5 h bei 170°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen wird ein Polyamingemisch erhalten, das neben dem überschüssigen MXDA hauptsächlich das Monoamid der Formel

    Figure 00110001
    enthält.57.4 g (421.6 mmol) of m-xylylenediamine (MXDA) and 25 g (84.3 mmol) of methyl oleic acid are mixed and stirred at 170 ° C. for 5 h, during which methanol is distilled off. After cooling, a polyamine mixture is obtained which, in addition to the excess MXDA, mainly the monoamide of the formula
    Figure 00110001
    contains.

    Beispiel 5Example 5

    55,5 g (407,3 mMol) MXDA und 15,0 g (81,5 mMol) Gallussäuremethylester werden vermischt und während 3 h bei 160°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 66,1 g (97% d. Th.) eines grüngelben Oels erhalten, das neben dem überschüssigen MXDA hauptsächlich das Monoamid der Formel

    Figure 00110002
    enthält.55.5 g (407.3 mmol) of MXDA and 15.0 g (81.5 mmol) of methyl gallic acid are mixed and stirred at 160 ° C. for 3 h, during which methanol is distilled off. After cooling, 66.1 g (97% of theory) of a green-yellow oil are obtained which, in addition to the excess MXDA, mainly the monoamide of the formula
    Figure 00110002
    contains.

    Dieses Produkt kann wie folgt gereinigt und isoliert werden:
    2,2 g des oben erhaltenen grüngelben Öles werden zweimal mit je 40 ml Dioxan ausgekocht, wobei jeweils die Dioxanphasen heiss abdekantiert werden. Durch Abkühlen der Dioxanphasen, Abdekantieren und Trocknen im Hochvakuum werden Rückstände erhalten (total 840 mg), die gemäss 1H-NMR- und Massenspektren aus der Verbindung der oben angegebenen Formel (zu etwa 67 Mol-%) und MXDA (zu etwa 33 Mol-%) bestehen (2:1-Molekülkomplex).    This product can be cleaned and isolated as follows:
    2.2 g of the green-yellow oil obtained above are boiled out twice with 40 ml of dioxane, the dioxane phases being decanted off hot. By cooling the dioxane phases, decanting and drying under high vacuum, residues are obtained (total 840 mg) which, according to 1 H-NMR and mass spectra, consist of the compound of the above formula (about 67 mol%) and MXDA (about 33 mol -%) exist (2: 1 molecular complex).

    Beispiel 6Example 6

    Eine Mischung von 20,0 g (58,7 mMol) Stearinsäurebutylester, 40,0 g (293,6 mMol) MXDA und 25,7 g Benzylalkohol wird während 15 h bei 200°C gerührt, wobei ein Teil des entstehenden Butanols abdestilliert wird. Nach dem Abkühlen werden 83,1 g (>100% d. Th.) eines halbfesten Produktegemisches erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen MXDA hauptsächlich das Monoamid der Formel

    Figure 00120001
    enthält.A mixture of 20.0 g (58.7 mmol) of stearic acid butyl ester, 40.0 g (293.6 mmol) of MXDA and 25.7 g of benzyl alcohol is stirred at 200 ° C. for 15 h, during which part of the butanol formed is distilled off . After cooling, 83.1 g (> 100% of theory) of a semi-solid product mixture are obtained, which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MXDA, mainly the monoamide of the formula
    Figure 00120001
    contains.

    Beispiel 7Example 7

    Eine Mischung von 18,0 g (61,6 mMol) 3-[3,5-Bis-(tert.-butyl)-4-hydroxyphenyl]-propionsäuremethylester, 42,0 g (307,8 mMol) MXDA und 25,7 g Benzylalkohol wird während 8 h bei 180°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 82,1 g (98% d.Th.) eines gelben Oels erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen MXDA hauptsächlich das Monoamid der Formel

    Figure 00120002
    enthält.A mixture of 18.0 g (61.6 mmol) of methyl 3- [3,5-bis (tert-butyl) -4-hydroxyphenyl] propionate, 42.0 g (307.8 mmol) of MXDA and 25, 7 g of benzyl alcohol are stirred at 180 ° C. for 8 hours, during which methanol is distilled off. After cooling, 82.1 g (98% of theory) of a yellow oil are obtained, which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MXDA, mainly the monoamide of the formula
    Figure 00120002
    contains.

    Beispiel 8Example 8

    Ein Gemisch von 10,0 g (54,3 mMol) Gallussäuremethylester, 37,0 g (217,2 mMol) Isophorondiamin (IPD) und 20,14 g Benzylalkohol wird während 3 h bei 160°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 63,6 g (97% d. Th.) eines dunklen Oels erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen IPD hauptsächlich die Monoamide der Formeln

    Figure 00130001
    enthält.A mixture of 10.0 g (54.3 mmol) of methyl gallate, 37.0 g (217.2 mmol) of isophoronediamine (IPD) and 20.14 g of benzyl alcohol is stirred at 160 ° C. for 3 hours, during which methanol is distilled off. After cooling, 63.6 g (97% of theory) of a dark oil are obtained, which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess IPD, mainly contains the monoamides of the formulas
    Figure 00130001
    contains.

    Beispiel 9Example 9

    57,5 g (337,3 mMol) IPD und 20,0 g (67,5 mMol) Oelsäuremethylester werden vermischt und während 6 h bei 170°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 76,3 g (>100%) eines Produktegemisches erhalten, das neben dem überschüssigen IPD hauptsächlich aus den Monoamiden der Formeln

    Figure 00140001
    besteht.57.5 g (337.3 mmol) of IPD and 20.0 g (67.5 mmol) of methyl oleic acid are mixed and stirred at 170 ° C. for 6 h, during which methanol is distilled off. After cooling, 76.3 g (> 100%) of a product mixture are obtained which, in addition to the excess IPD, mainly consists of the monoamides of the formulas
    Figure 00140001
    consists.

    Beispiel 10Example 10

    Ein Gemisch aus 15,0 g (44,0 mMol) Stearinsäurebutylester, 37,5 g (220,2 mMol) IPD und 22,5 g Benzylalkohol wird während 20 h bei 200°C gerührt, wobei ein Teil des entstandenen Butanols abdestilliert wird. Nach dem Abkühlen werden 71,4 g (>100% d. Th.) eines Produktegemisches erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen IPD hauptsächlich die Produkte der Formeln

    Figure 00140002
    enthält. A mixture of 15.0 g (44.0 mmol) of stearic acid butyl ester, 37.5 g (220.2 mmol) of IPD and 22.5 g of benzyl alcohol is stirred at 200 ° C. for 20 hours, part of the butanol formed being distilled off . After cooling, 71.4 g (> 100% of theory) of a product mixture is obtained which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess IPD, mainly contains the products of the formulas
    Figure 00140002
    contains.

    Beispiel 11Example 11

    Ein Gemisch von 15,0 g (51,3 mMol) 3-[3,5-Bis-(tert.-butyl)-4-hydroxyphenyl-]-propionsäuremethylester, 43,7 g (256,5 mMol) IPD und 25,2 g Benzylalkohol wird während 8,5 h bei 180°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 79,3 g (96%) eines gelben Oels erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen IPD hauptsächlich die Produkte der Formeln

    Figure 00150001
    enthält.A mixture of 15.0 g (51.3 mmol) of methyl 3- [3,5-bis (tert-butyl) -4-hydroxyphenyl -] - propionate, 43.7 g (256.5 mmol) of IPD and 25 , 2 g of benzyl alcohol is stirred at 180 ° C for 8.5 h, during which methanol is distilled off. After cooling, 79.3 g (96%) of a yellow oil are obtained, which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess IPD, mainly contains the products of the formulas
    Figure 00150001
    contains.

    Beispiel 12Example 12

    211,34 g (657,25 mMol) Ancamine® X2168 (MPCA) und 101,5 g Benzylalkohol werden auf 160°C erwärmt. Nach Zugabe von 25 g (164,31 mMol) 4-Hydroxybenzoesäuremethylester wird das Gemisch während 8 h bei 180°C gerührt, wobei Methanol abdestilliert wird. Nach dem Abkühlen werden 328,84 g (99%) eines Produktegemisches erhalten, das aus 30 Gew.-% Benzylalkohol und 70 Gew.-% eines Polyamingemisches besteht, das neben dem überschüssigen MPCA hauptsächlich die Monoamide der Formeln

    Figure 00160001
    sowie deren Struktur- und Stereoisomere enthält.211.34 g (657.25 mmol) of Ancamine® X2168 (MPCA) and 101.5 g of benzyl alcohol are heated to 160 ° C. After addition of 25 g (164.31 mmol) of methyl 4-hydroxybenzoate, the mixture is stirred for 8 hours at 180 ° C., methanol being distilled off. After cooling, 328.84 g (99%) of a product mixture are obtained which consists of 30% by weight of benzyl alcohol and 70% by weight of a polyamine mixture which, in addition to the excess MPCA, mainly contains the monoamides of the formulas
    Figure 00160001
    as well as their structural and stereoisomers.

    AnwendunnsbeispieleApplication examples Beispiel IExample I

    2,5 g des Härters gemäss Beispiel 1 werden mit 5,0 g Bisphenol A-diglycidylether mit einem Epoxidgehalt von 5,25 - 5,40 Äquivalenten/kg und einer Viskosität von 10000 - 12000 mPa·s gründlich vermischt. Das klare Gemisch wird mittels Pinsel auf eine sandgestrahlte, entfettete Stahlplatte oder mittels Rakel (0,20 mm) auf eine Glasplatte aufgetragen. Nach wenigen Stunden bei 20°C entstehen klare, harte Schichten, die auf der Glasplatte nach einem Tag bei 20°C eine Persoz-Härte von 266 s aufweisen, gemessen mit einem Pendeldämpfungsprüfer TY 5853 (BYK-Chemie) nach Persoz. Nach einer Durchhärtung während 7 Tagen bei 20°C ist die Persoz-Härte auf 326 s gestiegen. Die Schicht auf der Stahlplatte widersteht dann einer Belastung durch Benetzung mit 10%iger wässriger Essigsäure während mindestens drei Monaten, ohne Löcher zu bilden oder sich abzulösen.
    Das oben beschriebene härtbare Gemisch härtet auch bei 20°C/ 100% relativer Luftfeuchtigkeit sowie bei 5°C/45% relativer Luftfeuchtigkeit befriedigend aus, wobei keine oder nur eine sehr geringe Oberflächentrübung auftritt.    2.5 g of the hardener according to Example 1 are mixed thoroughly with 5.0 g of bisphenol A diglycidyl ether with an epoxy content of 5.25-5.40 equivalents / kg and a viscosity of 10,000-12,000 mPa · s. The clear mixture is applied with a brush to a sandblasted, degreased steel plate or with a squeegee (0.20 mm) on a glass plate. After a few hours at 20 ° C, clear, hard layers are formed that have a Persoz hardness of 266 s on the glass plate after one day at 20 ° C, measured with a TY 5853 pendulum damping tester (BYK-Chemie) according to Persoz. After hardening for 7 days at 20 ° C, the Persoz hardness rose to 326 s. The layer on the steel plate then resists exposure to 10% aqueous acetic acid for at least three months without pitting or peeling off.
    The curable mixture described above also cures satisfactorily at 20 ° C./100% relative atmospheric humidity and at 5 ° C./45% relative atmospheric humidity, with no or very little surface haze occurring.

    Beispiel IIExample II

    2,0 g des Härters gemäss Beispiel 1 und 0,5 g des Härters gemäss Beispiel 2 werden zusammen mit 5,0 g Bisphenol A-diglycidylether mit einem Epoxidgehalt von 5,25 - 5,40 Äquivalenten/kg und einer Viskosität von 10000 - 12000 mPa·s und 0,5 g 4-Nonylphenol gründlich vermischt. Das klare Gemisch wird mittels Pinsel auf eine sandgestrahlte, entfettete Stahlplatte oder mittels Rakel (0,20 mm) auf eine Glasplatte aufgetragen. Nach wenigen Stunden bei 20°C entstehen klare, harte Schichten, die auf der Glasplatte nach einem Tag bei 20°C eine Persoz-Härte von 165 s aufweisen, gemessen mit dem Pendeldämpfungsprüfer TY 5853 (BYK-Chemie) nach Persoz. Nach einer Durchhärtung während 7 Tagen bei 20°C ist die Persoz-Härte auf 268 s gestiegen. Die Schicht auf der Stahlplatte widersteht dann einer Belastung durch Benetzung mit 10%iger wässriger Essigsäure während mindestens drei Monaten, ohne Löcher zu bilden oder sich abzulösen. Das oben beschriebene härtbare Gemisch härtet auch bei 20°C/100% relativer Luftfeuchtigkeit sowie bei 5°C/45% relativer Luftfeuchtigkeit befriedigend aus, wobei keine oder nur eine sehr geringe Oberflächentrübung auftritt.2.0 g of the hardener according to Example 1 and 0.5 g of the hardener according to Example 2 together with 5.0 g bisphenol A diglycidyl ether with an epoxy content of 5.25 - 5.40 Equivalents / kg and a viscosity of 10,000 - 12,000 mPas and 0.5 g of 4-nonylphenol thoroughly mixed. The clear mixture is brushed onto a sandblasted, degreased steel plate or applied to a glass plate using a squeegee (0.20 mm). After A few hours at 20 ° C, clear, hard layers are formed, which then appear on the glass plate have a Persoz hardness of 165 s measured at one day at 20 ° C Pendulum damping tester TY 5853 (BYK-Chemie) according to Persoz. After hardening Persoz hardness rose to 268 s during 7 days at 20 ° C. The layer on the Steel plate then resists exposure to wetting with 10% aqueous Acetic acid for at least three months without pitting or peeling off. The curable mixture described above also cures at 20 ° C / 100% relative Air humidity as well as at 5 ° C / 45% relative air humidity no or only very slight surface clouding occurs.

    Wird in der oben angegebenen Formulierung das 4-Nonylphenol weggelassen, werden nach 1 Tag bei 20°C eine Persoz-Härte von 233 s, nach 7 Tagen bei 20°C eine Persoz-Härte von 297 s erreicht. Die sonstigen erwähnten Eigenschaften, insbesondere die Resistenz gegen 10%ige wässrige Essigsäure, sind sehr ähnlich.If the 4-nonylphenol is omitted in the formulation given above, after 1 day at 20 ° C a Persoz hardness of 233 s, after 7 days at 20 ° C one Persoz hardness of 297 s reached. The other properties mentioned, in particular the Resistance to 10% aqueous acetic acid are very similar.

    Beispiel IIIExample III

    2,5 g des Härters gemäss Beispiel 3 werden zusammen mit 3,8 g Bisphenol A-diglycidylether mit einem Epoxidgehalt von 5,25 - 5,40 Äquivalenten/kg und einer Viskosität von 10000 - 12000 mPa·s und 1,0 g 4-Nonylphenol gründlich vermischt. Das klare Gemisch wird mittels Pinsel auf eine sandgestrahlte, entfettete Stahlplatte oder mittels Rakel (0,20 mm) auf eine Glasplatte aufgetragen. Nach wenigen Stunden bei 20°C entstehen klare, harte Schichten, die auf der Glasplatte nach einem Tag bei 20°C eine Persoz-Härte von 52 s aufweisen, gemessen mit dem Pendeldämpfungsprüfer TY 5853 (BYK-Chemie) nach Persoz. Nach 7 Tagen Durchhärtung bei 20°C ist die Persoz-Härte auf 204 s gestiegen. Die Schicht auf der Stahlplatte widersteht dann einer Belastung durch Benetzung mit 10%iger wässriger Essigsäure während mindestens drei Monaten, ohne Löcher zu bilden oder sich abzulösen.
    Das oben beschriebene härtbare Gemisch härtet auch bei 20°C/100% relativer Luftfeuchtigkeit sowie bei 5°C/45% relativer Luftfeuchtigkeit befriedigend aus, wobei keine oder nur eine sehr geringe Oberflächentrübung auftritt.
    Wird in der obigen Formulierung das 4-Nonylphenol durch 0,5 g Benzylalkohol ersetzt, werden nach 1 Tag bei 20°C eine Persoz-Härte von 32 s, nach 7 Tagen von 255 s erreicht. Die sonstigen erwähnten Eigenschaften, insbesondere die Resistenz gegen 10%ige wässrige Essigsäure, sind sehr ähnlich.     2.5 g of the hardener according to Example 3 together with 3.8 g of bisphenol A diglycidyl ether with an epoxy content of 5.25 - 5.40 equivalents / kg and a viscosity of 10000 - 12000 mPa · s and 1.0 g 4 -Nonylphenol mixed thoroughly. The clear mixture is applied with a brush to a sandblasted, degreased steel plate or with a squeegee (0.20 mm) on a glass plate. After a few hours at 20 ° C, clear, hard layers are formed that have a Persoz hardness of 52 s on the glass plate after one day at 20 ° C, measured with the TY 5853 pendulum damping tester (BYK-Chemie) according to Persoz. After 7 days of curing at 20 ° C, the Persoz hardness rose to 204 s. The layer on the steel plate then resists exposure to 10% aqueous acetic acid for at least three months without pitting or peeling off.
    The curable mixture described above also cures satisfactorily at 20 ° C./100% relative atmospheric humidity and at 5 ° C./45% relative atmospheric humidity, with no or very little surface haze occurring.
    If the 4-nonylphenol in the above formulation is replaced by 0.5 g of benzyl alcohol, a Persoz hardness of 32 s is achieved after 1 day at 20 ° C. and 255 s after 7 days. The other properties mentioned, in particular the resistance to 10% aqueous acetic acid, are very similar.

    Beispiel IVExample IV

    2,5 g des Härters gemäss Beispiel 12 werden zusammen mit 5,05 g Bisphenol A-diglycidylether mit einem Epoxidgehalt von 5,25 - 5,40 Äquivalenten/kg und einer Viskosität von 10000 - 12000 mPa·s und 2,0 g 4-Nonylphenol gründlich vermischt. Das klare Gemisch wird mittels Pinsel auf eine sandgestrahlte, entfettete Stahlplatte oder mittels Rakel (0,20 mm) auf eine Glasplatte aufgetragen. Nach wenigen Stunden bei 20°C entstehen klare, harte Schichten, die auf der Glasplatte nach einem Tag bei 20°C eine Persoz-Härte von 86 s aufweisen, gemessen mit dem Pendeldämpfungsprüfer TY 5853 (BYK-Chemie) nach Persoz. Nach 7 Tagen Durchhärtung bei 20°C ist die Persoz-Härte auf 197 s gestiegen. Die Schicht auf der Stahlplatte widersteht dann einer Belastung durch Benetzung mit 10%iger wässriger Essigsäure während mindestens drei Monaten, ohne Löcher zu bilden oder sich abzulösen.
    Das oben beschriebene härtbare Gemisch härtet auch bei 20°C/100% relativer Luftfeuchtigkeit sowie bei 5°C/45% relativer Luftfeuchtigkeit befriedigend aus, wobei keine oder nur eine sehr geringe Oberflächentrübung auftritt.
    Wird in der obigen Formulierung das 4-Nonylphenol durch 0,5 g Benzylalkohol ersetzt, werden nach 1 Tag bei 20°C eine Persoz-Härte von 83 s, nach 7 Tagen von 292 s erreicht. Die sonstigen erwähnten Eigenschaften, insbesondere die Resistenz gegen 10%ige wässrige Essigsäure, sind sehr ähnlich.    2.5 g of the hardener according to Example 12 together with 5.05 g of bisphenol A diglycidyl ether with an epoxy content of 5.25 - 5.40 equivalents / kg and a viscosity of 10000 - 12000 mPa · s and 2.0 g 4 -Nonylphenol mixed thoroughly. The clear mixture is applied with a brush to a sandblasted, degreased steel plate or with a squeegee (0.20 mm) on a glass plate. After a few hours at 20 ° C, clear, hard layers are formed which have a Persoz hardness of 86 s on the glass plate after one day at 20 ° C, measured with the TY 5853 pendulum damping tester (BYK-Chemie) according to Persoz. After 7 days of curing at 20 ° C, the Persoz hardness rose to 197 s. The layer on the steel plate then resists exposure to 10% aqueous acetic acid for at least three months without pitting or peeling off.
    The curable mixture described above also cures satisfactorily at 20 ° C./100% relative atmospheric humidity and at 5 ° C./45% relative atmospheric humidity, with no or very little surface haze occurring.
    If the 4-nonylphenol in the above formulation is replaced by 0.5 g of benzyl alcohol, a Persoz hardness of 83 s is achieved after 1 day at 20 ° C. and 292 s after 7 days. The other properties mentioned, in particular the resistance to 10% aqueous acetic acid, are very similar.

    Claims (9)

    1. A monocarboxamide of the formula I
      Figure 00220001
      in which R is a radical of the formula
      Figure 00220002
      C9-C19alkyl, C9-C19alkenyl or a C9-C19alkdienyl,
      where each R2 independently of the other is a hydrogen atom or a C1-C4alkyl, each R3 independently of the others is a hydrogen atom or a hydroxyl group and at least one R3 is a hydroxyl group, and R1 is a radical of the formula
      Figure 00230001
    2. A monocarboxamide according to claim 1, wherein R in the formula I is a radical of the formula
      Figure 00230002
      a C15-C17alkyl or C15-C17alkenyl, in which each R2 is a tert-butyl and each R3 is a hydrogen atom or a hydroxyl group.
    3. A monocarboxamide according to claim 1, wherein R in the formula I is the radical of the formula
      Figure 00230003
    4. A monocarboxamide according to claim 1, wherein R1 in the formula I is a radical of the formula
      Figure 00230004
      Figure 00240001
    5. A monocarboxamide according to claim 1 of one of the formulae
      Figure 00240002
      or a structural isomer or stereoisomer thereof.
    6. A curing agent for expoxy resins, which comprises at least one compound of the formula I according to claim 1.
    7. A curing agent for epoxy resins according to claim 6, which is obtained by reacting a monocarboxylic acid or an ester thereof, of the formula II R-COOR4 in which R has the same meaning as in formula I and R4 is a hydrogen atom, alkyl or phenyl, with a di- or triamine of the formula III H2N-R1 in which R1 has the meaning as in formula I, at an elevated temperature, employing from 2 to 20 mol of a compound of the formula III per mole of a compound of the formula II.
    8. A curable mixture comprising
      (a) an epoxy resin having more than one 1,2-epoxide group in the molecule and
      (b) a compound of the formula I according to claim 1.
    9. A shaped article or coating obtained by curing a mixture according to claim 8.
    EP95810037A 1994-01-28 1995-01-19 Monocarboxylic acid amides of polyamines Expired - Lifetime EP0665214B1 (en)

    Applications Claiming Priority (2)

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    CH268/94 1994-01-28
    CH26894 1994-01-28

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    EP0665214B1 true EP0665214B1 (en) 1998-04-15

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    JPH08339162A (en) * 1995-06-12 1996-12-24 Alpine Electron Inc Map plotting method
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    JP6519600B2 (en) * 2017-02-06 2019-05-29 日立化成株式会社 Epoxy resin molding material for sealing and electronic component device
    WO2022036099A1 (en) * 2020-08-12 2022-02-17 Zymergen Inc. Catechol modifiers for epoxy adhesives

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    US5280091A (en) * 1992-02-07 1994-01-18 Air Products And Chemicals, Inc. Epoxy resins cured with mixed methylene bridged poly(cyclohexyl-aromatic)amine curing agents

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